Composition containing metal deactivators and the method of preparing the same



June 9, 1942. E. R. WHITE ET AL 2,285,878

COMPOSITION CONTAINING METAL DEACTIVATORS AND THE METHOD OF PREPARING THE SAME Filed June 10, 1940 Qx ggzn obsorbzd ml, pzr 100 grams of oil 2ooo 0 IO 20 so 40 so so 70 Time of oxidafion, Hours Patented June 9, 1942 COMPOSITION CONTAINING METAL na- ACTIVATORS AND THE, METHOD OF PRE- mama THE SAME Ellis R. White, Albany, and Ernest L. Walters,

- with one or the other of these metals.

San Francisco, Calif., asslgnors to Shell Development Company, San Francisco, Call! a corporation of Delaware Application June 10, 1940, Serial No. 339,790 I 11 Claims.

This invention relates to a method for the stabilization of organic substances and particularly to the protection of organic substances against deterioration by oxidationwhich is catalyzed by the presence of or by contact with certain oxidation promoters. An important application of this invention resides in the reduction of the amount of gum formed in gasoline during storage due to the presence of small amounts of certain metals, their compounds or both. Another application is as a stabilizer for lubricating oils to retard discoloration and sludge formation, etc., due to catalytic oxidation.

It is the purpose of this invention to provide a class of deactivator compounds which reduce the catalytic efiect of metal oxidation promoters,

more particularly of copper, iron, chromium, lead and the compounds of copper, chromium and lead. It is another purpose to provide deactivators which when added to organic substances will remain active for a considerable length of time when subjected to oxidizing influences. Still another purpose is to render hydrocarbon oils insensitive to the .catalytic oxidation of metals such as iron and copper for invariably, during theiruseful life, the oils come in contact -Organic substances normally contact metals, or frequently contain small amounts of metals usually dissolved in the form of a soluble salt,

and it has been observed that the presence oftremely diificult, it is often not possible to elim-- inate this troublesome catalyst of the oxidation reaction.

It has already been suggested to reduce the susceptibility of organic substances to oxidation induced by the presence of copper, by adding .to the organic substance certain deactivators which have the property of'rendering'the copper inactive. The deactivators heretofore suggested, comprise products of condensation of one mol of an aliphatic or aromatic primary diamine with two mols of salicylaldehyde or similar compounds. It is known for example, that the addition of these deactivators reduces the gumformation in the presence of dissolved copper as determined by the A. S. T. M. air jet method and also increases the induction period as tested by the Voorhees and Eisinger method described in S. A. E. J. 24,584 (1929).

It has been discovered that products obtained by reacting compounds of the general formula the carbonyl and primary amine radicals, possess the property of deactivating metallic iron, copper, chromium, lead and the compounds of copper, chromium and lead. Many of these products retain their activity after exposure to oxidizing influences.

The action of our deactivators appears to be specific for certain metals and their compounds. Diflerent types of organic substances may be protected from the catalytic effect of metal oxidation promoters. The deactivators must be at least slightly soluble in the organic substance by itself or in a mutual solvent. Neutral and basicsubstances are in general more susceptible to the action of the deactivators than acids. The general formula above covers diacyl compounds, or more specifically beta diketones wherein R1,. Ra, and Ra represent radicals selected from the group consisting of hydrogen, alkyl, aryl or aralkyl radicals, preferably containing a total of not more than 20 carbon atoms.

Suitable diacyl compounds are, for example, acetyl acetone, propionyl acetone, acetyl butyryl methane, acetyl isobutyryl methane, acetyl caproyl methane, 2 methyl 1.3 propane-dione, 2

ethyl 3.5 heptane-dione, acetyl aceto phenone, propionyl aceto phenone, butyryl aceto phenone," 'isobutyryl aceto phenone, phenyl acetyl acetone,

phenyl propionyl acetone, etc.

Amines capable of forming deactivators with the above diacyl compounds comprise certain aliphatic and carbocyclic diand higher polyamines.

The aliphatic poly-amines may be any aliphatic amine containing from 2 to 12 carbon atoms, which may be arranged in a continuous or discontinuous chain, and contain at least two primary amino groups directly attached to different carbon atoms. The carbon chain may contain oxygen, sulfur or nitrogen and the amino groups may be attached to carbon atoms which are interconnected by oxygen, sulfur or nitrogen linkages.

Suitable aliphatic amines are, for example, ethylene diamine, 1.2 propylene diamine, 1.3 propylene diamine, 1.10 decylene diamine, tetra methyl 1.2 diamino ethane, diethyl dimethyl 1.2

' oxygen,-sulfuriori nitr of adiacyl compound: Thus this-invention contain ats lea'st two radicals as. =.Io1lows: is r v wherein diamino ethane, 1.4 diamine diisobutyl, 1.6 diamino diisoamyl, diamino isopropanol, diamino butanols, diamino pentanols, diamino diethyl ether, amino ethyl amino propyl ether, corresponding thio or imino ethers, etc.

Suitable aryl-aliphatic amines are those in which ,oneiprimary amino group is connected to an aromatic nucleus through a linkage com prising at least one carbon atom. Additional primary amino radicals may be, attached to different carbon atoms of the same linkage or forming difierent linkages with the aromatic nucleus. Carbon linkages may consist of continuous or It is desirable that'the compounds of this invention have molecular weights which are not excessively high because the reaction between the deactivator compounds and the metal is apparently one in which one molecule of a symmetric deactivator is capable of capturing and deactidiscontinuous carbon chains which may contain ogen. Suitable carbocyclic amines arm for rins'tanoe;-'diamino diethyl-benf 1 'zene,- aminfoi eth-yl' amino propyl benzene, phenyl dia'mino ethanev -phenyl amino ethyl amino ethyl ether, phenyl amino ethyl amino ethyl thioether, phenyl amincrethyi aminopropylether, sat

- 1 *The reactionl compounds'of thlsinventionlare products formedeby-thereaction of 'one-mol of a poly-amino vcompound with at least twomols all; compounds of yinationtotvan oxygen atom. from ai-beta dicar-- -,bonyl'-compound;or:-the general formula Y 31 R: if

wherein R1, Raland R3 represent radicals select-' ed-iroin' the g'roup consisting of hydrogengalk'yl,

arylor aralkyl'radicals containing not moiethan a" total of carbonzatoms; Z represents, an an 4 epresentsi a radical derived by elimv vating not more than one atom of a metal. 7 It is therefore desirable to keep load in the molecule of the deactivators to a min Some deactivators are active primarily before oxidation while others are effective both before and after oxidation. 7

The efiectiveness of various compounds as metal deactivatorsand suppressors of oxidation catalyzed bymet'als may be estimated by measuring their activities under at least two conditions, namely before and after oxidation.

Thus, for example, as applied to a gasoline, one may measure first, the extent to which these compounds overcome the adverse eflect of them'etal in lowering the induction period; isecond, the extent to which they reduce the initial copper dish gum 1 accelerated oxidation.

value of the gasoline; and third, the extent to which they maintainlow copper dish gum after i Toillustrate how the metal deactivators of this invention suppress the catalytic activity, for

phatic oran-"aryl-alipha'tic radical of not'more than 12 carbon atoms which may contain hydroxy orp'rimary amino'radicals and ether, thioether and imlno ether linkages andn is 2 or more.

In analogy to: the above compounds wherein n is 2; we-"m'ay-also'use mixed compounds which containone dicarbonyl radical as shown above while another dicarbonyl radical. is replaced by a salicylal radical'of the type described in the copending application Serial No, 339,508, filed 'June 8, 1940. 'Suchmixed compounds may, for

example, be obtained by reacting a mixture of beta 'diketone and salicylaldehyde with one of the bolyamines described'earlier. v

A typical deactivator is the product prepared by reacting 2 mols of acetyl aceto phenone with one mol of ethylene diamine and yielding dibenzoyl acetonyl ethylene diamine'.

lubricating oil is illustrated by the attached example of copper, the deactivators were tested in gasoline containing 1 part per million, of dissolved copper in the form of copper phenyl propionatei. The results of tests are shown in Table I:

efiect of the deactivators in contact with drawing representing a graph wherein is plotted the length of time in hours of oxidation against the amount ofbxygen absorbed in the presence of "metallic iron. v

In this test, the oil is exposed to'pure oxygen at atmospheric pressure and at a temperature of 150 C; r I

On the ordinate of the graph is plotted the mols of oxygen absorbed, on the abscissa is indicated the time of-oxidation. Two curves are shown, curve I representing the art of oxygen absorption in the absence oi. anydeactivator and curve 2 representing the rate of oxygen absorption under identicalconditions in the presence of 0.1% by weight of diacetyl acetonyl ethylene diamine. 7 up It will be seen that the metallic ironwas deactivated for a considerable length of time under vthe extremely severe conditions of the test.

- Our d'eactivators also suppress the catalytic oxidation which may be caused by a combination of the various metal oxidation promoters. Thus, for example, if gasoline containing dissolved copper is stored in an iron drum, our compounds deiarctivate both the dissolved copper and metallic the amount of dead Our products are active in various organic substances which are subject to deterioration by oxidation and which substances during their useful life come in contact with any of the metals or their compound hereinbefore enumerated. Thus, various refined and semi-refined hydrocarbon oils may be stabilized, such as gasoline, kerosene, special boiling point solvents, Diesel fuels, spray oils, lubricating oils, etc., pure hydrocarbons such as benzene, toluene, various liquid olefins, etc. Other substances capable of being protected are, for example, animal fats and oils, vegetable fats and oils, soaps, photographic developers, both natural and synthetic sulfonated and sulfated oils, essential oils, perfumes, cellulose acetate, rubber, various resins, etc.

The presence of antioxidants and-other 'compounds in the substance to be desensitized, which tergents, etc., or in'Diesel fuels together with knock suppressors, anti-oxidants, etc. It is, how-' ever, desirable that the addition agent shall not raise the acidity of the substance to. be desensitized to the point of greatly diminishing the activity of the deactivators.

The amounts of our deactivators to be added to the substances effectively to suppress the catbeing susceptible to the inhibiting 7 reaction product.

water by interacting not more than one of the carbonyl radicals of each molecule of the dicarbonyl compound with a primary amino radical, said beta. dicarbonyl compounds having the general formula i i t wherein R1, R2 and Rarepresent radicals selected from the group consisting of hydrogen, alkyl, aryl and aralkyl radicals containing a total of not "more than 20 carbon atoms said reaction product being at. least slightly'soluble in said organic substance and said organic substance action of said 2. The substance or claim 1 which contains .01% to 1% by weightof the reaction product. 3. .An organic substance subject to deterioration thru oxidation, which substance during its useful life comes in-c'ontact with an oxidation promoter selected from the group consisting of metallic iron, copper, chromium, lead and compounds of copper, chromiumand-lead'containing a small amount of a deactivator having the general formula aiytic action of the metals or their compounds.

will naturally vary with the stability requirements of the treated product, as well as with the amount of metal contained in the organic substance if dissolved metal is the source of the instability. In general, quantities ranging from about .01% to 1% are useful and provide the necessary protection, although under certain circumstances, amounts outside of these limits may be used.

The metal deactivators may be added to the organic substance to be stabilized in any desired form. They may be added in solid or liquid form, mixed with other addition agents or dissolved in a solvent. 7

Some organic substances dissolve metals during their use. This, for instance, is the case with lubricating oils, electrical oils, gasolines, etc. When treating such substances with our compounds, it is often desirable to use an amount considerably in excess of that which is required to .give it adequate initial protection. In such cases, the proper amounts of the deactivator may if desired be added during the use of the organic substance as may be required from time to metallic iron, copper, chromium, lead'and compounds of copper, chromium and lead, containing a small amount of a reaction product of an aliphatic poly primary amine having 2 to 12 carbon atoms with two mols of a beta dicarbonyl compound formed by the elimination of wherein Y represents aradical: derived by elimination of an oxygen atom from a beta. dicarbonyl compound of the general formula wherein R1, R2 and Ra'represent radicals selected from the-group consisting of hydrogen, alkyl, aryl andfaralkyl radicals containing no more than a total of 20'carbon atoms, Z represents an aliphatic-radicalof-notmore than 12 carbon atoms and 711. is integer ,of "2 or -more said deactivator being 811 1188517 slightly soluble useful" life comes" in Contact with an oxidation wherein Z represents an aliphatic radical .having 2 to 12 carbon" atoms and containing alinkage of an element selected from the group consisting of oxygen, nitrogen and sulfur, Y represents a radical derived by elimination of an I oxygen atom from a beta dicarbonyl compound ofthe general formula a, a, a,

wherein R1, R2 and R3 represent radicals selected from the group consisting of hydrogen, alkyl, aryl and aralkyl radicals containing a total of not more than 20 carbon atoms and n is either 2, or more said deactivator being at least slightly soluble in said organic substance and said organic substance being susceptible to the action of said deactivator.

5. An organic substance subject to deterioration thru oxidation, which substance during its taining a small amount of diacetyl acetonyl ethylene diamine.

6. An organic substance subject to deterioration thru oxidation, which substance during its useful life comes in contact with an oxidation promoter selected from the group consisting of metallic iron, copper, chromium, lead and compounds of copper, chromium and lead, is capable of dissolving dibenzoyl acetonyl'ethylene diamine and is susceptible to its deactivating action containing a small amount of dibenzoyl acetonyl ethylene diamine.

7. A gasoline of reduced copper dish gum containing a small amount of a reaction product of an aliphatic poly primary amine having 2 to 12 carbon atoms with two mols of a beta dicarbonyl compound formed by the elimination of water by interacting not more than one of the carbonyl radicals of each molecule of the dicarbonyl compound with a primary amino radical, and said beta dicarbonyl compounds having the general formula tit wherein R1, R1 and R: represent radicals selected from the group consisting of hydrogen, alkyl, aryl and aralkyl radicals containing a total of not more than 20 carbon atoms said reaction product being at least slightly soluble in said gasoline.

8. A lubricating oil of improved oxidation stability in contactwith iron comprising a mineral lubricating oil containing a small amount of a reaction product of an aliphatic poly primary amine having 2 to 12 carbon atoms with two mols of a beta dicarbonyl compound formed by the elimination of water by interacting not more than one of the carbonyl radicals of each molecule of the dicarbonyl compound with a primary amino radical, said beta dicarbonyl compounds having the general formula R: R: R:

(fl i wherein R1, R2 and R3 represent radicals selected from the group consisting of hydrogen, alkyl, aryl and aralkyl radicals containing a total of not more than 20 carbon atoms said reaction productbeing at least slightly soluble in said lubricating oil.

mula

wherein R1, R2 and R3 represent radicals selected from the groupconsisting of hydrogen, alkyl, aryl and aralkyl radicals containing a total of not more than 20 carbon atomssaid reaction product being at least slightly soluble in said organic compound and said organic compound being susceptible to the deactivating action of said reaction product.

l0. The method of prolonging the useful life of lubricating oil normally subject to deterioration through oxidation promoters selected from the group consisting of metallic iron, copper,

chromium lead and compounds of copper, chromium and lead, comprising adding from time to time during use of the oil small amounts'of a reaction product of an aliphatic poly primary amine having 2 to 12 carbon atoms with two mols of a beta dicarbonyl compound formed by the elimination of water by interacting not more than one of the carbonyl radicals of each molecule of the dicarbonyl compound with a primary amino radical, said beta dicarbonyl compounds having the general formula it I II H 0 wherein R1, R2 and R: represent radicals selected from the, group consisting of hydrogen, alkyl, aryl and aralkyl radicals contain a total of not more than 20 carbon atoms said re- ELLIS R. WHITE. ERNEST L. WALTERS. 

